Norcamphanyl esters of alpha, beta-unsaturated dicarboxylic acids and polymers thereof



rates lhdddfi 'l Patented June 12, 1962 3,6383%! NORCAMYPHANYL ESTERS OFa,B-UNSATU- D'LCARBQXYLTC AClll d AND ?LY- MERS THEREUF llohn R.Qaldwell, Winston It. .lacirson, In, and Edward H. Hill, ldingspurt,TGSHL, assignors to Eastman Kodak Company, Rochester, N.Y., acorpnration of New lersey No Drawing. Filed Mar. 12, 1959, Ser. No.798,518 6 Claims. (Cl. 269-435) This invention relates to norcamphanylesters of :,5- monoethylenically unsaturated aliphatic dicarboxylicacids, and more particularly to such esters of maleic, fumaric anditaconic acids, to polymers thereof, and to the preparation of the same.

It is known that unsaturated bicyclic alcohols such as 2,5-endomethyleneA tetrahydrobenzyl alcohol can be condensed with mdunsaturateddicarboxylic acids to give esters containing several ethylenic linkageswhich on polymerization give thermosetting resins. Accordingly, suchresins have but limited utility. We have now found that by employing asaturated bicyclic alcohol, for example, norcamphanyl alcohols with ad-unsaturated dicarboxylic acids, the resulting esters contain but asingle ethylenic linkage and are readily polymerizable to thermoplasticresins having a wide variety of uses.

The new class of unsaturated esters of the invention are represented bythe following general formulas:

1 H H C R, o 0 Rt 0 \I H H I R-CH C(GHQ) O C CHI-CH6 0 (CH2) "-0 CH-RCH2 CH2 1 R-Cl-l CH1 l'lzC GHR o G H H and 11 H r s /x c oomfinro lGEL-R CH2 H2O CH--R G l H IT. 0 R1 C H l C 'C X01 2) n-C CHR OH: I HacCH-R c H wherein n represents an integer of O or 1, each R representsthe same member such as an atom of hydrogen or an alkyl group of 14carbons such as methyl, ethyl, propyl, isopropyl, butyl, etc. groups,and each R represents the same member such as an atom of hydrogen or amethyl group. These monomers are useful as chemical intermediates forthe preparation of various derivatives thereof and are especiallyvaluable as intermediates for preparing resinous thermoplastic polymersthat are useful for the manufacture of films, fibers, sheets, tubes,molded obiects and as oil additives. Such resinous thermoplasticpolymers are soluble in common organic solvents such as carbontetrachloride, chloroform, benzene, toluene, mineral oils, tertiarybutyl alcohol, higher esters of phthalic acid, etc., but insoluble insolvents such as water, acetone, methanol, acetonitrile, cellosolve, andthe like. They vary from soft gums represented by the homopolymers tomaterials having melting points up to about 250 C. represented byvarious copolymers which on molding give clear, hard molded objects orflexible, tough films, fibers and sheets.

It is, accordingly, an object of the invention to provide unsaturatedesters represented by the above Formulas I and 11. Another object is toprovide useful thermoplastic polymers of the same. Another object is toprovide polymeric materials that have utility as oil additives, asfilmand fiber-forming materials and as molding compositions. Anotherobject is to provide processes for the preparation of the monomers andpolymers thereof. Other objects will become apparent hereinafter.

In accordance with the invention, we prepare our new monomeric compoundsby refluxing one molecular proportion of a dicarboxylic acid such asmaleic acid, fumaric acid, itaconic acid, maleic anhydride, etc. with atleast two molecular proportions of a hydroxycamphanyl compoundrepresented by the general formula:

wherein n, R and R are as previously defined, in an inert hydrocarbonmedium such as benzene, toluene, xylene, etc., in the presence of anacidic catalyst such as sulfuric or toluenesulfonic acids. The waterformed in the reaction is removed, for example, as the benzene azeotropeand collected in a Dean-Stark trap. The reaction is completed when nomore excess of the alcohol is advantageously employed to ensurecompletion of the reaction. Esterification can also be carried out byheating the acid or anhydride, the alcohol (in excess) and the acidiccatalyst for several hours at C in an autoclave. However, the previouslydescribed method employing benzene as the reaction medium is preferredprimarily because higher yields are obtained and less 0 alcohol isrequired.

The polymerizations for preparing the resinous thermoplastic polymers ofthe invention may be carried out conveniently in an organic solvent suchas one of the lower alcohols, ketones or esters or in a hydrocarbon suchas benzene, toluene or hexane. Mass or bulk polymerizations may also beused. The polymerizations can also be carried out by dispersing themonomers in water and adding suitable dispersing agents. Catalysts, beatand actinic light accelerate the reactions. Suitable catalysts that canbe used alone or in admixture include peroxides such as benzoylperoxide, acetyl peroxide, lauroyl peroxide, tertiary butylhydroperoxide, hydrogen peroxide, etc, persulfates such as sodium,potassium and ammonium persulfates, perborates such as sodium andpotassium perborates, etc. AZobis-isobutyronitrile may also be employedas a catalyst. The amount of catalyst used can vary from about 0.1 to3.0%, based on the Weight of monomer to be polymerized. The temperaturecan vary over a wide range e.g. from 20-l30 'C., but preferably thepolymerizations are carried out at from about 50- 70 C. Thepolymerizations can be carried out by batch or continuous processes atatmospheric or higher pressures. If desired, an inert atmosphere such asnitrogen can be maintained in the reaction vessel. When carried out in anonsolvent medium such as water, an activating agent such as an alkalimetal bisulfite e.g. sodium or potassium bisulfite may advantageously beemployed. Also, it is advantageous in an aqueous system to employsurface active agents such as fatty alcohol sulfates e.g. sodium orpotassium cetyl sulfate, sodium or potassium lauryl sulfate, etc.,aromatic sulfonates eg sodium or potassium salts of alkylnaphthalenesulfonic acid, sulfonated oils, and the like. These surface activeagents may be employed up to about 3-5% of the weight of the monomer tobe polymerized. If desired, a chain regulator such as an alkyl mercaptane.g. hexyl, cetyl, lauryl, myristyl, etc. mercaptans, can be employed.

proportions can be employed, are from 10-90% the invention by weight Ingeneral, the resulting coethyl,

methylstyrene, p-acetaminostyrene, etc., vinyl idene halides e.g. vinylchloride, vinyl fluoride, vinylidene chloride, vinylidene fluoride,etc., tetrafluoroethylene, chloro-trifluoroethylene, N-vinyl imides suchas N- vinyl succinimide, N-vinyl phthalimide, etc., N-vinyl lactams e.g.N-v-inyl pyrrolidone, -vinyl piperidone, etc., a-olefins containing from2-8 carbon atoms e.g. ethylene,

The following examples will serve to illustrate further the newmonomers, polymers thereof and the manner of their preparation and uses.

fluxed for 48 hours.

reaction was collected a short Vigreux column. The benzene solution wascooled, washed With sodium bicarbonate solution, dried HO O O O I I 0(5H 5 e i/ l/ EXAMPLE 2 A mixture containing 116 g. (1.0 mole) offumaric acid, 258 g. (2.05 moles) of Z-norcamphanemethanol, 300 ml. ofbenzene and g. of p-toluenesulfonic acid was refluxed for 13 hours. aDean-Stark trap attached After the reaction mixture was worked up as inExample 1, the product was recrystallized give 290 g. (87% 82 C, ofbis(2-norcarnphanylmethyl) fumarate represented by the followingstructural formula:

Hcooocm I I -om0oiicn L h I/ Bis(2norcamphanyl) maleate was preparedfrom maleic acid and Z-norcamphanol according to the procedure ofExample 1. is ester was a colorless liquid, B.P. l-l98 C./2 mm.

EXAMPLE 4 Bis(2-norcamphanylmethyl) maleate was prepared anhydride andZ-norcamphanemethanol ac- Example 1. This ester was a colorless liquid,B.P. 206209 C./3 mm.;

1.5073 EXAMPLE 5 .Bis(2-methyl-2-norcamphanyl) maleate was prepared frommaleic anhydride and Z-methyI-Z-norcamphanol acprocedure of Example 1.This ester disstilled at 202-206 C./2 mm.

EXAMPLE 6 Bis(2,3-dimethyl-2-norcamphanylmethyl) maleate was preparedfrom maleic anhydride and 2,3-dimethyl-2-normg to the procedure ofExample 2 This ester distilled at 204 206 C./3 mm.

EXAMPLE 8 A mixture of 25 g. of bis(2-norcamphanylmethyl) th 11k EXAMPLE9 A mixture of 16.5 g. (0.05 mole) of-bis(2-norcamphanylmethyl)fumarate, (0.05 mole) stearate, ml. oftert.-butyl alcohol and 0.5 g.

acetonitrile several times. 91%. It consisted of approximately 51%recurring units of the f of the polymer molecule being recurring unitsof the vinyl stearate component.

The above polymer was tested as an oil. The table below compares itsadditive in mineral performance with g. of ammonium acrylic resin oiladditive).

Table Viscosity in centistokes ASTM Viscosity slope index The firstcolumn shows the difference in viscosity of the oil at two difierenttemperatures, with and without the specified additives. The secondcolumn is an indication of the rate of change of the viscosity withtemperature. A small numerical value is desirable. The viscosity indexof the last column is an empirical number indicating the effect ofchange of temperature on the viscosity of an oil. A low viscosity indexsignifies a relatively large change of viscosity with temperature. Thus,it will be seen that the copolymer of above Example 6 improves themineral oil in every case, and in addition shows superiority inproducing and maintaining a relatively higher viscosity over thetemperature range of 100-210 C. than shown by the comparison samples.

EXAMPLE 10 Using the method of preparation, purification and oiladditive testing of Example 9, a gum-like copolyrner prepared from amixture of 23.4 g. (0.075 mole) of bis- (2-norcamphanyl)fumarate, 15.5g. (0.075 mole) of vinyl stearate, 200 ml. tert.-butyl alcohol and 0.5g. of benzoyl peroxide showed a viscosity value of 28.87 at 100 C. and5.03 at 210 C., an ASTM slope of 0.73 and a viscosity index of 112.1.

EXAMPLE 11 bis(2-norcamphanylmethyl) 200 ml. of toluene and 0.4 g.tumbled in a pressure A mixture of 8 g. of fumarate, 32g. of styrene, ofaZo-bis-isobutyronitrile was bottle at 70 C. for 24 hours. A clear,viscous dope was obtained which was poured into acetonitrile toprecipitate the polymer. After separation and drying, the copolyrnerproduct weighed 37.6 g. It consisted of approximately by weight ofrecurring units of bis(2- norcamphanylmethyl) fumarate, the remainder ofthe copolymer molecule being recurring styrene units, and wasthermoplastic. On compression molding, the copolymer gave clear, hardmolded objects.

EXAMPLE 12 A mixture of 23.4 g. (0.075 mole) of bis(2-norcamphanyl)maleate, 7.5 g. (0.075 mole) of isopropenyl acetate, 100 ml. oftert.-butyl alcohol and 0.3 g. of benzoyl peroxide was heated at refluxin a 250-ml. flask for A clear, viscous dope was obtained which wasacetonitrile to precipitate the copolymer. the copolymer product weighed29.4 g. It contained approximately 76% by weight of recurring units ofbis(2-norcamphanyl) maleate, the remainder of the copolyrner moleculebeing recurring isopropenyl units, and was thermoplastic. It was usefulprimarily as an additive to synthetic lubricants.

EXAMPLE 13 A mixture of 5 g. of bis(2-norcamphanylmethyl) maleate, 35 g.of vinyl acetate, 400 ml. of water, 0.4 persuliate, 0.2 g. of sodiumbisulfite and 0.4 g. of sulfonated mineral oil was tumbled in a pressurebottle at 55 C. for 20 hours. A milky emulsion of copolymer was obtainedfrom which clear, flexible films were readily cast.

After drying,

EXAMPLE 14 A mixture of 5 g. of bis(6-methyl-2-norcamphanyl) fumarate,45 g. of methyl methacrylate, 300 ml. of acetone and 0.5 g. of acetylperoxide was tumbled in a pressure bottle at 60 C. for 10 hours. Theresulting copolymer contained approximately 10% by weight of the abovefumarate component. It was isolated by evaporating the solvent. A yieldof 48.8 g. of copolyrner was obtained. It was thermoplastic and moldedreadily to give clear, hard molded objects.

EXAMPLE 15 A mixture of 10 parts by weight of bis(2-norcamphanylmethyl)fumarate and parts by weight of acrylonitrile was added slowly over aperiod of one hour at 60 C. to a stirred solution containing by weight400 parts water, 1 part of potassium persulfate, 0.5 part of sodiumbisuliite and 2 parts of lauryl alcohol sulfate. At the end of 6 hours,the copolymer containing approximately 10% by weight of the fumaratecomponent was isolated by pouring the emulsion into a 20% solution ofsodium sulfate, washed and dried. The yield was 97 g. of copolyrner. Ithad a softening point of approximately 225-230 C. A dope of thecopolymer in dimethylformamide was wet-spun into fibers which afterdrafting had a tenacity of 3.2 g./ denier and an elongation of 18%.

EXAMPLE 16 EXAMPLE 17 A mixture of 90 g. of bis(2-norcamphanyl)fumarate, 10 g. of vinyl stearate, 500 ml. of tert.-butyl alcohol and1.0 g. of aZo-bis-isobutyronitrile was tumbled in a pressure bottle at60 C. for 24 hours. The copolyrner was isolated by pouring intoacetonitrile and purified as described in above Example 9. It containedapproximately 90% by weight of the above fumarate component, theremainder of the copolyrner molecule the vinyl stearate component. Thisproduct was readily soluble in mineral oil and was useful as an oiladditive.

EXAMPLE 18 A mixture of 20 g. of bis(6-methyl-2-norcamphanyl) itaconate,50 g. of vinyl acetate, 200 ml. of tert.-butyl alcohol and 0.5 g. ofbenzoyl peroxide was refluxed for 10 hours in a flask equipped w'th areflux condenser. The resulting copolymer was obtained by precipitatingthe reaction mixture into methanol. A yield of 61 g. of a soft gum wasobtained. it contained approximately 28% by weight of the above fumaratecomponent and was readily soluble in chloroform.

By proceeding as described in the above examples, other of the mentionedmonomers and corresponding polymers thereof can be prepared. Where thepolymers are gum-like in character, these are generally useful asmineral oil additives and as plasticizing agents, and in cases where aresolids as in the case of certain copolyrners these are useful forpreparing films, sheets and molded objects. The copolymers withacrylonitrile containing at least 70% of the acrylonitrile component areparticularly useful for the preparation of filaments and fibers. Thepolymers of the invention can be extruded from their melts or cast fromsolutions thereof in appropriate solvents. Those polymers givingflexible tough films are also useful as photographic film supportmaterials. Suitable fillers, dyes, pigments, softening agents, etc. canbe incorporated, if desired, into the copoly mer compositions.

The invention has been described in detail ticular reference What weclaim is: 1. A thermoplastic copolymer of from -90% weight of anunsaturated ester selected from those resented by the following generalformulas:

H H ll l! (OHQ)DOCCH=CHCO(CHZ)DC on atoms, styrene,

v1nyl chloride.

versely from 10 0 b 4 A thermoplastic copolymer of from 10-90% weight ofbis(6-methyl-2-norcamphanyl) fumarate and conversely from 90-10% byweight of methyl metha'crylate.

5. A thermoplastic copolymer of from 10-90% by weight ofibis(Z-norcamphanylmethyl) fumarate and con- Weight ofbis(6-methyl-2-norcamphanyl) itaconate and conversely from 90-1*0% byWeight of vinyl acetate.

References Cited in the file of this patent UNITED STATES PATENTS

1. A THERMOPLASTIC COPOLYMER OF FROM 10-90% BY WEIGHT OF AN UNSATURATEDESTER SELECTED FROM THOSE REPRESENTED BY THE FOLLOWING GENERAL FORMULAS: